CN1176113C - silicobridged binuclear metallocene zirconium compound - Google Patents

silicobridged binuclear metallocene zirconium compound Download PDF

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CN1176113C
CN1176113C CNB001096974A CN00109697A CN1176113C CN 1176113 C CN1176113 C CN 1176113C CN B001096974 A CNB001096974 A CN B001096974A CN 00109697 A CN00109697 A CN 00109697A CN 1176113 C CN1176113 C CN 1176113C
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connects
zirconium compounds
silicon bridge
binuclear metallocene
siosime
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CN1276386A (en
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徐善生
周秀中
王佰全
田公路
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Nankai University
China Petrochemical Corp
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Nankai University
China Petrochemical Corp
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Abstract

The present invention relates to the synthesis of a metallocene compound which has the general formula (I), wherein R=H or Me4; E=Me2SiOSiMe2, Me2SiSiMe2 or Me2SiOSiMe2OSiMe2. The bilithium salt of a ligand is dropwise added to the THF solution of monocyclopentadienyl zirconium trichlorid, the solution stays overnight at room temperature, and reaction products are separated and purified with a solvent. The metallocene compound is matched with MAO for use; when used as a catalyst of the polymerization of ethylene and propylene, the metallocene compound has high catalytic activity, and the activity reaches more than 18.0kg PE/mmol. Zrh.

Description

Silicon bridge connects binuclear metallocene zirconium compounds and synthetic method and application
Technical field
The present invention relates to the synthetic of metallocene compound.
Background technology
The structure of metallocene compound that has been used for vinyl polymerization and propylene polymerization is as shown below:
Figure C0010969700031
Macromol.Symp.1997，118，129
Polyhedron 1998，17(7)1055
Organometallics，1989，8，2107
Once reported that single silicon bridge connected synthesizing in toluene of binuclear metallocene zirconium compounds long-time the backflow and obtains the long part of other bridge and then can not get binuclear compound.
Summary of the invention
The invention provides a kind of silicon bridge and connect binuclear metallocene zirconium compounds and synthetic method and application, its general formula is:
Figure C0010969700032
Wherein, Rn=1～4H, E=Me 2SiOSiMe 2Me 2SiSiMe 2Me 2SiOSiMe 2OMe 2
Rn＝1～4Me，E＝Me 2SiOSiMe 2；Me 2SiOSiMe 2OMe 2。
The silicon bridge of hydrolysis connects the binuclear metallocene zirconium compounds:
Rn＝1～4Me。6
The present invention utilizes two lithium salts with part to be added drop-wise in the THF solution of single luxuriant tri-chlorination zirconium (mol ratio 1: 2), ambient temperature overnight, and through separating, solvent is purified, and has successfully synthesized the binuclear compound of a series of different bridges length.Its synthetic method is as follows:
Figure C0010969700042
E＝Me 2SiSiMe 2 1
Me 2SiOSiMe 2 2
Me 2SiOSiMe 2OSiMe 2 3
Figure C0010969700043
E＝Me 2SiOSiMe 2 4
Me 2SiOSiMe 2OSiMe 2 5
The present invention and MAO are used, and are used for the catalyzer of ethene and propylene polymerization, the catalytic activity height, and its activity reaches more than the 18.0kgPE/mmol.Zrh..
Embodiment
Synthesizing of example 1 compound 1:
In 100mL Schlenk bottle, add 1,2-two (cyclopentadienyl) tetramethyl-disilane 1.07g (4.35mmol) and 20mL THF.(2.0N, hexane solution 8.7mmol) add back stirring at room 2h, get pink pair of lithium salts suspension to drip 4.35mL n-BuLi under 0 ℃ of stirring.
In 100ml Schlenk bottle, add 3.54g (8.7mmol) CpZrCl 32THF, 20ml THF and 20mlDME after stirring makes it to dissolve fully, are cooled to 0 ℃, and the above-mentioned two lithium salts suspension that make are transferred to wherein with steel pipe.Room temperature reaction spends the night.Suction filtration is washed with a small amount of cold THF, gets the 1.41g white solid, and this solid is used 50mL CH in the Sha Shi extractor 2Cl 2Extract 24h.Extracting solution is separated out white small-crystalline.Suction filtration is used a small amount of CH 2Cl 2Wash, get 1.25g (41%) white micro-crystals 1.
Synthesizing of example 2 compounds 2:
In the 100mL Schlenk bottle, add 3.35g (8.23mmol) CpZrCl 32THF, 40mL THF and 20mLDME, 0 ℃ drips 4.3mmol[O (Me 2SiCpLi) 2] ++THF solution.Room temperature reaction spends the night, and is heated to 50 ℃, reaction 1h, and vacuum is removed all solvents, adds 20ml CH in the residue 2Cl 2With 10mL 6N HCl, tell organic phase, use anhydrous MgSO 4Dry.Filter, the filtrate rotary evaporation is removed all solvents, a small amount of Et of residue 2The O washing gets the 1.80g white solid.This crude product CH 2Cl 2/ Et 2The O recrystallization gets the colourless tabular crystal 2 of 1.52g.
With same that method can synthesize 3,4,5.
Synthesizing of example 3 compounds 6:
Add 1.28g (1.83mmol) 1 and 75ml CH in the 100mL round-bottomed bottle 2Cl 2, stir into suspension, add 0.33mL (3.66mmol) aniline and 0.033mL (1.83mmol) H 2O, room temperature reaction spends the night.Filter, the filtrate rotary evaporation is removed all solvents, and residual white solid washes twice with a small amount of sherwood oil, uses CH then 2Cl 2/ sherwood oil recrystallization gets 0.76g white needle-like crystals 6.Table 1～4 are relevant analysis and aggregated data of compound 1～6.
Table 1 compound 1～6 analytical data
Compound Molecular formula Color Productive rate (%) Ultimate analysis reality (theory)
C(％) H(％)
1 C 24H 30Cl 4Si 2Zr 2 white solid 41 40.98(41.24) 4.70(4.33)
2 C 24H 30Cl 4OSi 2Zr 2 white solid 51 40.35(40.32) 3.85(4.23)
3 C 26H 36Cl 4O 2Si 3Zr 2 white solid 30 39.24(39.58) 4.57(4.60)
4 C 32H 46Cl 4OSi 2Zr 2 white solid 15 46.15(46.41) 5.50(5.61)
5 C 34H 52Cl 4O 2Si 3Zr 2 white solid 11 44.95(45.31) 5.64(5.82)
6 C 24H 30Cl 2OSi 2Zr 2 white solid 64 44.45(44.76) 4.60(4.70)
Table 2 compound 1～6 1H NMR data
Compound δC 5H 5 δC 5H 4 δSi-CH 3 δC 5HMe 4
1 6.40(s，10) 6.48(t，4)， 6.41(t，4) 0.34(s，12)
2 6.44(s，10) 6.71(t，4)， 6.52(t，4) 0.36(s，12)
3 6.46(s，10) 6.74(t，4)， 6.52(t，4) 0.36(s，12) 0.07(s，6)
4 6.52(t，4)， 6.30(t，4) 0.32(s，12) 5.90(s，2) 1.99(s，12) 1.96(s，12)
5 6.56(t，4)， 6.30(t，4) 0.35(s，12) -0.04(s，6) 5.94(s，2) 2.00(s，12) 1.96(s，12)
6 6.31(s) 6.28(s)，10H 6.66(m)，6.56 (m)，6.49(m)， 6.40(m)，6.18 (m)，8H 0.42(s)，.0.40 (s)，0.35(s)，12 H
Table .3 compound 1～5 mass-spectrometric data
Compound. MS (m/e, intensity %)
1 644(12，[M-Cl-Me] +)，579(65，[M-3Cl] +)，559(6)，350(16)，312 (100，[(C 5H 5)(C 5H 4SiMe 2)ZrCl] +)，293(53)，220(27)
2 675(4，[M-Cl] +)，595(65，[M-3Cl] +)，575(8)，293(100， [(C 5H 5)(C 5H 4SiMe 2O)Zr] +)，
3 679(5，[M-3Cl] +)，459(100，[M-Cp 2ZrCl 2-Cl] +)，407(60， Me 3Si 2O(C 5H 4) 2ZrCl 2) +)，349(99，[MeSiO(C 5H 4) 2ZrCl 2] +)，311(64， [Me 2Si(C 5H 4) 2ZrCl] +)，293(100，[(C 5H 5)(C 5H 4SiMe 2O)Zr] +)，225 (30，[CpZrCl 2] +)，73(48，Me 3Si +)
4 465(53)，405(64，[(C 5HMe 4)(C 5H 4SiMe 2)ZrCl 2] +)，389(92， [(C 5HMe 4)(C 5H 4SiMe 2)ZrCl 2-CH 4] +)，369(97， [(C 5HMe 4)(C 5H 4SiMe 2)ZrCl 2-HCl] +)，343(34， [(C 5HMe 4)(C 5H 4SiMe 2)ZrCl 2-CH 4-HCl] +)，297(36)，267(27)，249 (100，[(C 5H 4SiMe 2)ZrCl] +)，121(19，[C 5HMe 4] +)
5 539(28)，559(18)，465(55)，445(32)，423(27)，367(45)，349(26)， 321(51)，295(29)，249(100，[(C 5H 4SiMe 2)ZrCl] +)，121(43， [C 5HMe 4] +)
Example 4
The vinyl polymerization experiment is carried out in the 250mL there-necked flask of special strap clamp cover.This there-necked flask is loaded onto electronic stirring, uses N 2Gas fill row three times, charge into ethylene gas under the vacuum state, by the solenoid control system pressure a little more than 1atm.Add 100mL toluene, constant temperature 10min makes ethylene gas saturated.The toluene solution that adds MAO and catalyzer then successively, record distribution jar internal pressure is with the variation of polymerization time.Behind the polymerization certain hour, add 100mL acidifying ethanol (containing 10%HCl) termination reaction.Suction filtration is used the 100mL washing with alcohol.The polymkeric substance that obtains in 60 ℃ of vacuum-dryings to constant weight.Weigh, calculate catalytic activity.The molecular weight of polymkeric substance is measured with gel permeation chromatography (GPC).
Table 4 1～6/MAO vinyl polymerization data
Catalyzer Temperature (℃) Output (g) Active Mη(×10 -5) Mw/Mn
1 20 30 40 50 60 3.24 4.02 4.24 3.24 3.57 2.16 2.68 2.83 2.16 2.38 7.89 7.95 6.68 6.77 4.87 2.24 2.36 2.67 2.21 3.51
2 20 30 40 50 60 70 1.40 2.14 2.52 3.29 5.44 8.06 0.93 1.43 1.68 2.19 3.63 5.37 5.49 5.70 5.69 4.71 4.33 1.74 2.76 2.76 3.09 3.51 2.89 2.90
3 20 30 30 40 50 60 70 5.98 (a) 9.15 1.81 (b) 2.13 (b) 3.58 (b) 5.49 (b) 4.57 (b) 4.78 6.10 6.03 7.10 11.9 18.3 15.2 13.43 8.79 7.30 7.79 6.10 3.14 1.69 2.01 2.48 2.71 2.40 2.95 2.44 2.83
4 20 40 60 2.54 1.74 2.76 1.69 1.16 1.84 11.86 5.79 2.48 2.54 3.57 3.04
5 20 30 40 60 4.57 6.24 5.49 4.18 3.05 4.16 3.66 8.37 7.85 7.28 4.74 2.60 2.60 2.35 2.55 3.62
6 30 40 50 60 4.36 5.50 4.22 3.06 (d) 2.91 3.67 2.81 3.06 5.02 4.97 4.18 3.36 2.16 2.65 2.44 2.67
Polymerizing condition: [catalyzer .]=1.5 * 10 -6Mol; Al/Zr=2500; T=30min; 1atm.of monomer pressure; In 100mL toluene .a) .t=25min; B) .[Cat.]=0.30 * 10 -6C) .t=10min; D) .t=20min.
Active: (kgPE/mmolZrh); M η: g/mol, determined by GPC in o-C 6H 4Cl 2135 ℃ of at.

Claims (5)

1. a silicon bridge connects the binuclear metallocene zirconium compounds, it is characterized in that its general formula is:
Figure C001096970002C1
Wherein, Rn is 4H, and E is Me 2SiOSiMe 2, Me 2SiSiMe 2Or Me 2SiOSiMe 2OSiMe 2Or Rn is 4Me, and E is Me 2SiSiMe 2Or Me 2SiOSiMe 2OSiMe 2
2. a hydrolysis silicon bridge connects the binuclear metallocene zirconium compounds, it is characterized in that it is:
Figure C001096970002C2
Rn is 1H and 3Me.
3. the said silicon bridge of claim 1 connects the synthetic method of binuclear metallocene zirconium compounds, it is characterized in that its synthesis step is: with two lithium salts and single luxuriant tri-chlorination zirconium reaction, the mol ratio 1: 2 of part cyclopentadiene base silane, THF is a solvent, ambient temperature overnight is isolated product, uses CH 2Cl 2/ Et 2O purifies solid phase prod, gets final product.
4. the said hydrolysis silicon bridge of claim 2 connects the synthetic method of binuclear metallocene zirconium compounds, it is characterized in that its synthesis step is: at CH 2Cl 2The middle silicon bridge that adds connects binuclear metallocene zirconium compounds, aniline and H 2O, its mol ratio is 1: 2: 1, room temperature reaction spends the night, and removes all solvents, isolates product, uses CH 2Cl 2/ sherwood oil is purified solid phase prod and is got final product.
5. the said silicon bridge of claim 1 connects the binuclear metallocene zirconium compounds and is used for vinyl polymerization and propylene polymerization.
CNB001096974A 2000-06-22 2000-06-22 silicobridged binuclear metallocene zirconium compound Expired - Fee Related CN1176113C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8609793B2 (en) 2010-10-07 2013-12-17 Chevron Phillips Chemical Company Lp Catalyst systems containing a bridged metallocene
US8629292B2 (en) 2010-10-07 2014-01-14 Chevron Phillips Chemical Company Lp Stereoselective synthesis of bridged metallocene complexes
US8637616B2 (en) 2010-10-07 2014-01-28 Chevron Philips Chemical Company Lp Bridged metallocene catalyst systems with switchable hydrogen and comonomer effects

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101190923B (en) * 2006-11-29 2010-11-03 中国石油天然气股份有限公司 Asymmetric bridging dinuclear metallocene compound and its preparation and application in olefin polymerization
CN100420700C (en) * 2007-03-08 2008-09-24 山东轻工业学院 Bridged metallocene iso-dinulear catalyst and preparation method and application thereof
CN101638447B (en) * 2008-07-31 2011-10-05 中国石油天然气股份有限公司 Supported bis-silicon-bridged metallocene catalyst, preparation method and application thereof
CN103772545B (en) * 2012-10-23 2016-08-10 中国石油天然气股份有限公司 A kind of bridged rings pentadienyl bimetallic catalyst and application thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8609793B2 (en) 2010-10-07 2013-12-17 Chevron Phillips Chemical Company Lp Catalyst systems containing a bridged metallocene
US8629292B2 (en) 2010-10-07 2014-01-14 Chevron Phillips Chemical Company Lp Stereoselective synthesis of bridged metallocene complexes
US8637616B2 (en) 2010-10-07 2014-01-28 Chevron Philips Chemical Company Lp Bridged metallocene catalyst systems with switchable hydrogen and comonomer effects
US9018407B2 (en) 2010-10-07 2015-04-28 Chevron Phillips Chemical Company Lp Stereoselective synthesis of bridged metallocene complexes
US9040642B2 (en) 2010-10-07 2015-05-26 Chevron Phillips Chemical Company Lp Catalyst systems containing a bridged metallocene
US9040643B2 (en) 2010-10-07 2015-05-26 Chevron Phillips Chemical Company Lp Bridged metallocene catalyst systems with switchable hydrogen and comonomer effects

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